US4131740A - Alkyl perfluoro-ω-fluoroformyl esters and their preparation - Google Patents

Alkyl perfluoro-ω-fluoroformyl esters and their preparation Download PDF

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Publication number
US4131740A
US4131740A US05/789,724 US78972477A US4131740A US 4131740 A US4131740 A US 4131740A US 78972477 A US78972477 A US 78972477A US 4131740 A US4131740 A US 4131740A
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United States
Prior art keywords
formula
fluoride
compound
alkyl
cof
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US05/789,724
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English (en)
Inventor
David C. England
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EIDP Inc
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EI Du Pont de Nemours and Co
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US05/789,724 priority Critical patent/US4131740A/en
Priority to US05/868,615 priority patent/US4138426A/en
Priority to SE7803062A priority patent/SE436869B/sv
Priority to AU35165/78A priority patent/AU515564B2/en
Priority to CA301,618A priority patent/CA1130313A/en
Priority to JP53044909A priority patent/JPS6049176B2/ja
Priority to GB15526/78A priority patent/GB1593222A/en
Priority to ZA00782223A priority patent/ZA782223B/xx
Priority to MX173174A priority patent/MX149082A/es
Priority to MX197260A priority patent/MX172538B/es
Priority to BE186900A priority patent/BE866123A/xx
Priority to IT22497/78A priority patent/IT1094423B/it
Priority to SU782604925A priority patent/SU869555A3/ru
Priority to NZ187025A priority patent/NZ187025A/xx
Priority to FR7811504A priority patent/FR2387938A1/fr
Priority to BR7802432A priority patent/BR7802432A/pt
Priority to DE19782817366 priority patent/DE2817366A1/de
Priority to NLAANVRAGE7804228,A priority patent/NL187435C/xx
Application granted granted Critical
Publication of US4131740A publication Critical patent/US4131740A/en
Priority to CA000394206A priority patent/CA1144566A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C08F16/26—Monomers containing oxygen atoms in addition to the ether oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/60—Unsaturated compounds containing ether groups, groups, groups, or groups the non-carboxylic part of the ether being unsaturated

Definitions

  • This invention relates to fluorinated ⁇ -carboxylic- ⁇ -carbonyl fluorides and their preparation.
  • Fluoromonomers containing carboxyl or carboxylic ester groups such as described in U.S. Pat. No. 3,546,186, issued Dec. 8, 1970, have been difficult to prepare. Such monomers are useful in preparing fluorohomopolymers or copolymers with tetrafluoroethylene. Thus, it would be advantageous to be able to prepare fluoromonomers easily.
  • Also provided is a process for preparing ROOC--CF 2 --COF comprising: contacting SO 3 with a compound of the formula ROOC--CF 2 --CF 2 --OR 1
  • R and R 1 alike or different, are alkyl of 1-6 carbon atoms.
  • the compounds of the invention are fluorine-containing ⁇ -carboxylic- ⁇ -carbonyl fluorides of the formula ##STR4## in which R is alkyl of 1-6 carbon atoms, particularly methyl or ethyl and n is 0-6, preferably 0.
  • R is alkyl of 1-6 carbon atoms, particularly methyl or ethyl and n is 0-6, preferably 0.
  • n is 0-6, preferably 0.
  • the compound H 3 COOC--CF 2 --COF is most preferred.
  • the reaction of compounds of formula II with sulfur trioxide is exothermic and provision should be made for dissipating the heat of reaction.
  • One method is to add the alkoxyester compound of formula II in small portions to the SO 3 with cooling by reflux condenser or external cooling means.
  • the SO 3 can be added in small portions to the alkoxyester, but the former procedure is preferred.
  • the reaction can also be carried out on a continuous basis by slowly feeding the separate reactants into a cooled reaction zone from which product is continuously withdrawn.
  • Sulfur trioxide can be used either in monomeric form or polymeric form. The reaction is preferably carried out neat.
  • diluents which are relatively inert to SO 3 or which couple with SO 3 , e.g., dioxane, chloroform, carbon tetrachloride, fluorocarbon liquids and the like.
  • Temperatures at which the reaction is operable range from about -30° C. to about 250° C. and temperatures from about 0-100° C. are preferred.
  • Pressure is not a critical variable and pressure both below and above atmospheric pressure can be employed.
  • the molecular proportions in which SO 3 and the compounds of formula II can be brought together to carry out this reaction can be varied widely such as from about 1:20 to 20:1, preferably about 2 to 1.
  • the reaction of a compound of formula III with hexafluoropropylene oxide is preferably carried out in the presence of fluoride ion as a catalyst.
  • a suitable fluoride e.g., an alkali metal fluoride such as cesium fluoride, potassium fluoride; silver fluoride; ammonium fluoride; a tetraalkylammonium fluoride (alkyl of 1-4 carbons) such as tetramethylammonium fluoride, tetraethylammonium fluoride, and tetrabutylammonium fluoride, and sulfonium fluorides such as benzene sulfonium fluoride.
  • an alkali metal fluoride such as cesium fluoride, potassium fluoride
  • silver fluoride ammonium fluoride
  • a tetraalkylammonium fluoride alkyl of 1-4 carbons
  • sulfonium fluorides such
  • the fluoride catalyst is usually used in conjunction with an inert liquid diluent (preferably an organic liquid) in which the selected fluoride is at least 0.001% soluble.
  • the fluoride catalyst may be used in amounts from about 0.001 to about 1.0 molar equivalent per mole of the compound of formula III.
  • Suitable diluents include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and aprotic solvents such as acetonitrile.
  • the reaction is somewhat exothermic and provision for dissipation of the heat of reaction should be made. Temperatures employed can range from about -50° C. to about 200° C. with temperatures in the range of about -10 to about 80° C. being preferred.
  • Hexafluoropropylene oxide is a gas over much of the operable temperature range and pressures close to atmospheric pressure are preferred. Operable molar proportions of hexafluoropropylene oxide to the compounds of formula III can vary from about 1:20 to about 20:1, preferably about 1 to 1.
  • more than one mol of hexafluoropropylene oxide can react with a compound of formula III to yield compounds of formula V in which m is greater than one.
  • m molecular proportions of hexafluoropropylene oxide
  • pressures and lower temperatures are selected.
  • m e.g. 1 or 2
  • Each of the compounds of formula I is a reactive organic compound which is at once a carboxylic ester and an acid fluoride.
  • Such fluorinated compounds are rare, and understandably so because the known processes for synthesizing difunctional carboxylic compounds readily yield dicarboxylic esters as well as diacid fluorides but teach almost nothing about how to obtain compounds with both a carboxylic ester group and a carbonyl fluoride group in the same molecule. In carrying out reactions with compounds of formula I care must be taken to prevent their ready conversion to the more ordinary corresponding dicarboxylic esters or dicarbonyl fluorides.
  • the monomers of formula VI can be homopolymerized to heavy oils suitable as lubricants and can be copolymerized, for example, with tetrafluoroethylene or chlorotrifluoroethylene, to yield tough, solid polymers which are thermoplastic and capable of being hot pressed or rolled into sheets and films for wrapping uses, as protective layers where exceptional chemical stability is required and as ion exchange membranes in electrolysis cells.
  • polymers may be represented by the repeating unit ##STR8## in which p is 0 to 5, q is 0 to 20, the X's may be all fluorine or three fluorine and one chlorine and R' is H or lower alkyl.
  • the preferred copolymers have average compositions corresponding to those in which p is 1 or 2 and q is 1 to 9.
  • a 150 ml Carius tube was loaded with a mixture of 0.5 g each of CsF and KF (vacuum dried at 400° C.), 3 ml tetraglyme, 34.5 g H 3 COOC--CF 2 --COF and 60 g HFPO. The tube was sealed and rotated overnight at room temperature. Distillation of the reaction mixture yielded 15 g H 3 COOC--CF 2 --CF 2 --O--CF(CF 3 )-COF, b.p. 65° C./100 mm.
  • Powdered cesium fluoride (15 g) was placed in a 500 ml 4-necked flask, which was then plugged except for a connection to a manifold attached to a vacuum pump and open-end manometer. Vacuum was applied to the flask while it was heated with a Meeker burner to thoroughly dry the cesium fluoride. After the flask had cooled, dry nitrogen was admitted and then a large magnetic stirrer. The flask was fitted with a thermometer, reevacuated, filled with nitrogen and 20 ml of tetraglyme and 63 g (0.4 m) of H 3 COOCCF 2 COF added.
  • the flask was then cooled to -10° C., evacuated and filled to 600 mm pressure with hexafluoropropene epoxide (HFPO) three times. Stirring was started and the pressure of HFPO was maintained automatically at 600 mm by a vacuum regulator. The HFPO was absorbed steadily in an exothermic reaction and cooling was necessary to keep the temperature between 0° and -10° C. The reaction was stopped after 140 g (0.84 m) of HFPO had been absorbed.
  • HFPO hexafluoropropene epoxide
  • the low layer (190 g) was distilled.
  • the products obtained are tabulated below.
  • the ratio of products formed can be varied by the temperature of reaction and mainly by the amount of HFPO used.
  • Example 4 The procedure of Example 4 was repeated except that 182 g (1.17 m) of H 3 COOCCF 2 COF was used, no cooling was used (run at 55° C.) and the addition of HFPO was stopped after 190 g had been absorbed.
  • the copolymer was pressed at 250° C. under 500 psi to yield a 3 mil film which showed strong infrared absorption for ester carbonyl at 5.5 ⁇ .
  • This film was heated for 3 hours at 100° C. in a solution of 15 g KOH in 35 g water and 35 g dimethylsulfoxide (DMSO).
  • DMSO dimethylsulfoxide
  • Infrared examination of the resulting film showed the ester carbonyl band had been replaced by carboxylic acid absorption (broad at 2.8 ⁇ for --OH and at 5.95 ⁇ for C ⁇ O). This confirmed that a copolymer of the above repeating unit where q is greater than 1 was obtained.
  • Example A(4) Using the general procedure of Example A(4), six 20 ml Carius tubes were each charged with 0.01 ml of a 6% solution of perfluoropropionyl peroxide in 1,1,2-trichlorotrifluoroethane and the respective quantities of methyl 3-[2-(trifluoroethenoxy)-1-(trifluoromethyl)trifluoroethoxy]-tetrafluoropropionate (vinyl ether), tetrafluoroethylene (TFE) and 1,1,2-trichlorotrifluoroethane (solvent) indicated in the table below.
  • the tubes were sealed at liquid nitrogen temperature, rotated at room temperature overnight, cooled and opened. The respective amounts of copolymer were recovered by filtration, washed with ether and dried.
  • Example D(1) Using the general procedure of Example D(1) a 200 ml Carius tube containing 6 g (0.015 m) of 3-[2-(trifluoroethenoxy)-1-(trifluoromethyl)trifluoroethoxy]tetrafluoropropionic acid neutralized with a slight excess of 0.2N sodium hydroxide, 0.25 g ammonium persulfate in 10 ml water, 0.02 g Na 2 S 2 O 3 .5H 2 O in 10 ml water and 10 g tetrafluoroethylene was rotated overnight at room temperature and then cooled and opened. A gellike polymer (sodium salt) was collected by filtration and vacuum dried at 100° C.
  • sodium salt sodium salt

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US05/789,724 1977-04-20 1977-04-20 Alkyl perfluoro-ω-fluoroformyl esters and their preparation Expired - Lifetime US4131740A (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
US05/789,724 US4131740A (en) 1977-04-20 1977-04-20 Alkyl perfluoro-ω-fluoroformyl esters and their preparation
US05/868,615 US4138426A (en) 1977-04-20 1978-01-11 Alkyl perfluoro-ω-fluoroformyl esters and monomers therefrom
SE7803062A SE436869B (sv) 1977-04-20 1978-03-16 Forening till anvendning sasom mellanprodukt vid framstellning av fluorsubstituerade, polymeriserbara olefiniska foreningar innehallande karboxisyra- eller estergrupper samt forfarande for framstellning derav
AU35165/78A AU515564B2 (en) 1977-04-20 1978-04-17 Alkyl perfluoro-w-fluoroformyl esters and their preparation
JP53044909A JPS6049176B2 (ja) 1977-04-20 1978-04-18 弗素化α−カルボキシル−ω−カルボニルフルオライドの製造法
CA301,618A CA1130313A (en) 1977-04-20 1978-04-18 ALKYL PERFLUORO-.omega.-FLUOROFORMYL ESTERS, THEIR PREPARATION AND MONOMERS THEREFROM
BE186900A BE866123A (fr) 1977-04-20 1978-04-19 Fluorures alpha-carboxyles omega-carbonyles polyfluores et procede de preparation
ZA00782223A ZA782223B (en) 1977-04-20 1978-04-19 Alkyl perfluoro-w-fluorformyl esters and their preparation
MX173174A MX149082A (es) 1977-04-20 1978-04-19 Procedimiento para obtener esteres perfluoro-omega-fluoro formil alquilicos
MX197260A MX172538B (es) 1977-04-20 1978-04-19 Procedimiento para obtener esteres perfloro-omega-fluoro-formil alquilicos
GB15526/78A GB1593222A (en) 1977-04-20 1978-04-19 Perfluoroesters and their preparation
IT22497/78A IT1094423B (it) 1977-04-20 1978-04-19 Alchil perflucro omega fluoroformil esteri e loro praparazione
SU782604925A SU869555A3 (ru) 1977-04-20 1978-04-19 Способ получени сложных алкилперфтор- @ -фторформильных эфиров
NZ187025A NZ187025A (en) 1977-04-20 1978-04-19 Fluorinated alpha-carboxylic-omega-carbonyl fluorides
FR7811504A FR2387938A1 (fr) 1977-04-20 1978-04-19 Fluorures o-carbonyles a-carboxyles fluores et leur preparation
BR7802432A BR7802432A (pt) 1977-04-20 1978-04-19 Processo para preparar esteres de alquilperfluor-omega-fluorfor mila e compostos assim obtidos
NLAANVRAGE7804228,A NL187435C (nl) 1977-04-20 1978-04-20 Esters van gefluoreerde carbonzuren alsmede werkwijze voor het bereiden daarvan.
DE19782817366 DE2817366A1 (de) 1977-04-20 1978-04-20 Alkylperfluor-omega-fluorformylester und verfahren zu ihrer herstellung
CA000394206A CA1144566A (en) 1977-04-20 1982-01-14 Alkyl perfluoro-w-fluoroformyl esters, their preparation and monomers therefrom

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/789,724 US4131740A (en) 1977-04-20 1977-04-20 Alkyl perfluoro-ω-fluoroformyl esters and their preparation

Related Child Applications (2)

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US05/868,615 Continuation-In-Part US4138426A (en) 1977-04-20 1978-01-11 Alkyl perfluoro-ω-fluoroformyl esters and monomers therefrom
US05/934,615 Division US4247713A (en) 1978-08-17 1978-08-17 Alkyl perfluoro-ω-fluoroformyl esters and their preparation

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US05/868,615 Expired - Lifetime US4138426A (en) 1977-04-20 1978-01-11 Alkyl perfluoro-ω-fluoroformyl esters and monomers therefrom

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US (2) US4131740A (zh)
JP (1) JPS6049176B2 (zh)
AU (1) AU515564B2 (zh)
BE (1) BE866123A (zh)
BR (1) BR7802432A (zh)
DE (1) DE2817366A1 (zh)
FR (1) FR2387938A1 (zh)
GB (1) GB1593222A (zh)
IT (1) IT1094423B (zh)
MX (2) MX149082A (zh)
NL (1) NL187435C (zh)
NZ (1) NZ187025A (zh)
SE (1) SE436869B (zh)
SU (1) SU869555A3 (zh)
ZA (1) ZA782223B (zh)

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US4273728A (en) * 1979-03-14 1981-06-16 E. I. Du Pont De Nemours And Company Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4275225A (en) * 1979-03-14 1981-06-23 E. I. Du Pont De Nemours And Company Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4292449A (en) * 1979-03-14 1981-09-29 E. I. Du Pont De Nemours And Company Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4316986A (en) * 1980-09-23 1982-02-23 E. I. Dupont De Nemours & Company Preparation of difluoromalonyl fluoride
DE3130859A1 (de) * 1980-08-04 1982-04-22 E.I. du Pont de Nemours and Co., 19898 Wilmington, Del. Verfahren zur herstellung von perfluoro-(4,7-dioxa-5-methyl-8-fluoroformyl)-nonansaeurealkylester
US4334082A (en) * 1980-09-26 1982-06-08 E. I. Du Pont De Nemours And Company Dialkyl perfluoro-ω-fluoroformyl diesters and monomers and polymers therefrom
US4335255A (en) * 1980-04-03 1982-06-15 E. I. Du Pont De Nemours And Company Alkyl perfluoro (2-methyl-5-oxo-3-oxahexanoate)
US4349650A (en) * 1979-03-14 1982-09-14 E. I. Du Pont De Nemours And Company Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4360601A (en) * 1980-12-10 1982-11-23 E. I. Du Pont De Nemours And Company Process for extraction of fluorinated copolymers with fluorocarbons
US4385187A (en) * 1981-06-30 1983-05-24 E. I. Du Pont De Nemours And Company Perfluoroketovinyl ethers and copolymers therefrom
US4390720A (en) * 1981-10-14 1983-06-28 E. I. Du Pont De Nemours And Company Alkyl-ω-fluoroformyl ester and process
US4401711A (en) * 1981-01-16 1983-08-30 E. I. Du Pont De Nemours And Company Cation exchange membrane with high equivalent weight component
US4414159A (en) * 1980-09-26 1983-11-08 E. I. Du Pont De Nemours & Co. Vinyl ether monomers and polymers therefrom
US4420638A (en) * 1982-03-02 1983-12-13 E. I. Du Pont De Nemours And Company Fluorinated ether-ketones
US4434273A (en) 1981-06-30 1984-02-28 E. I. Du Pont De Nemours And Company Perfluoroketovinyl ethers and copolymers therefrom
US4440917A (en) * 1981-12-14 1984-04-03 E. I. Du Pont De Nemours & Company Vinyl ethers monomers and polymers therefrom
US4454247A (en) * 1981-12-14 1984-06-12 E. I. Du Pont De Nemours & Company Ion exchange membranes
US4474700A (en) * 1981-07-02 1984-10-02 E. I. Du Pont DeNemours and Company β-Substituted polyfluoropropionate salts and derivatives
US4591439A (en) * 1984-05-08 1986-05-27 E. I. Du Pont De Nemours And Company Ion exchange process and apparatus
US4686300A (en) * 1983-03-07 1987-08-11 E. I. Du Pont De Nemours And Company Polyfluoro gamma-ketoesters and 5-hydroxy gamma lactone analogues thereof
US5023362A (en) * 1980-04-03 1991-06-11 E. I. Du Pont De Nemours And Company Alkyl perfluoro(2-methyl-5-oxo-3-oxahexanoate)
US5919973A (en) * 1996-12-02 1999-07-06 Shin-Etsu Chemical Co., Ltd. Process for the polymerization of hexafluoropropene oxide
US6407282B1 (en) * 1999-11-04 2002-06-18 Nippon Mektron, Limited Process for producing monoester from dicarboxylic acid fluoride
US20040019237A1 (en) * 2002-05-14 2004-01-29 Cherstkov Victor Filippovich Fluorosulfates of hexafluoroisobutylene and its higher homologs
US20040176636A1 (en) * 2001-06-29 2004-09-09 Nobuto Hoshi Process for producing fluorinated vinyl ether
US9765008B2 (en) 2014-01-10 2017-09-19 Unimatec Co., Ltd. Perfluorovinyloxy polyether carboxylic acid alkali metal salt and method for producing the same
CN114402011A (zh) * 2019-09-13 2022-04-26 大金工业株式会社 含氟代聚醚基化合物及其制造方法

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US4209635A (en) * 1979-03-02 1980-06-24 Asahi Glass Company Limited Process for producing perfluorinated vinyl ether having ester group
US4608206A (en) * 1979-11-16 1986-08-26 E. I. Du Pont De Nemours And Company Fluorinated 3-ketoglutaroyl halides
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US5006259A (en) * 1988-03-21 1991-04-09 E. I. Du Pont De Nemours And Company Process and means for use of anaphylatoxin adsorbents
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US5134211A (en) * 1990-01-31 1992-07-28 E. I. Du Pont De Nemours And Company Hydroxy containing fluorovinyl compounds and polymers thereof
US5128014A (en) * 1991-03-01 1992-07-07 E. I. Du Pont De Nemours And Company Irradiation of cation exchange membranes
US5252193A (en) * 1991-11-04 1993-10-12 E. I. Du Pont De Nemours And Company Controlled roughening of reinforced cation exchange membrane
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US5330626A (en) * 1993-02-16 1994-07-19 E. I. Du Pont De Nemours And Company Irradiation of polymeric ion exchange membranes to increase water absorption
US5824749A (en) * 1994-10-04 1998-10-20 Nippon Mektron, Limited Fluorine-containing elastomer composition
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JP3599390B2 (ja) * 1994-11-04 2004-12-08 日本メクトロン株式会社 パーフルオロ不飽和ニトリル化合物およびその製造法
US5637748A (en) * 1995-03-01 1997-06-10 E. I. Du Pont De Nemours And Company Process for synthesizing fluorinated nitrile compounds
JP3223776B2 (ja) * 1995-03-31 2001-10-29 日本メクトロン株式会社 含フッ素エラストマー組成物
US5919878A (en) * 1996-09-13 1999-07-06 E. I. Du Pont De Nemours And Company Amorphous fluoropolymer containing perfluoro(ethyl vinyl ether)
US5969067A (en) * 1996-09-13 1999-10-19 E.I. Dupont De Nemours And Company Phosphorus-containing fluoromonomers and polymers thereof
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US4349650A (en) * 1979-03-14 1982-09-14 E. I. Du Pont De Nemours And Company Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4273728A (en) * 1979-03-14 1981-06-16 E. I. Du Pont De Nemours And Company Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4275225A (en) * 1979-03-14 1981-06-23 E. I. Du Pont De Nemours And Company Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4292449A (en) * 1979-03-14 1981-09-29 E. I. Du Pont De Nemours And Company Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4273729A (en) * 1979-03-14 1981-06-16 E. I. Du Pont De Nemours And Company Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US5023362A (en) * 1980-04-03 1991-06-11 E. I. Du Pont De Nemours And Company Alkyl perfluoro(2-methyl-5-oxo-3-oxahexanoate)
US4335255A (en) * 1980-04-03 1982-06-15 E. I. Du Pont De Nemours And Company Alkyl perfluoro (2-methyl-5-oxo-3-oxahexanoate)
DE3130859A1 (de) * 1980-08-04 1982-04-22 E.I. du Pont de Nemours and Co., 19898 Wilmington, Del. Verfahren zur herstellung von perfluoro-(4,7-dioxa-5-methyl-8-fluoroformyl)-nonansaeurealkylester
US4345092A (en) * 1980-08-04 1982-08-17 E. I. Du Pont De Nemours And Company Process for alkyl perfluoro(4,7-dioxa-5-methyl-8-fluoroformylnonanoate
US4316986A (en) * 1980-09-23 1982-02-23 E. I. Dupont De Nemours & Company Preparation of difluoromalonyl fluoride
US4414159A (en) * 1980-09-26 1983-11-08 E. I. Du Pont De Nemours & Co. Vinyl ether monomers and polymers therefrom
US4334082A (en) * 1980-09-26 1982-06-08 E. I. Du Pont De Nemours And Company Dialkyl perfluoro-ω-fluoroformyl diesters and monomers and polymers therefrom
US4360601A (en) * 1980-12-10 1982-11-23 E. I. Du Pont De Nemours And Company Process for extraction of fluorinated copolymers with fluorocarbons
US4401711A (en) * 1981-01-16 1983-08-30 E. I. Du Pont De Nemours And Company Cation exchange membrane with high equivalent weight component
US4385187A (en) * 1981-06-30 1983-05-24 E. I. Du Pont De Nemours And Company Perfluoroketovinyl ethers and copolymers therefrom
US4434273A (en) 1981-06-30 1984-02-28 E. I. Du Pont De Nemours And Company Perfluoroketovinyl ethers and copolymers therefrom
US4474700A (en) * 1981-07-02 1984-10-02 E. I. Du Pont DeNemours and Company β-Substituted polyfluoropropionate salts and derivatives
US4390720A (en) * 1981-10-14 1983-06-28 E. I. Du Pont De Nemours And Company Alkyl-ω-fluoroformyl ester and process
US4454247A (en) * 1981-12-14 1984-06-12 E. I. Du Pont De Nemours & Company Ion exchange membranes
US4440917A (en) * 1981-12-14 1984-04-03 E. I. Du Pont De Nemours & Company Vinyl ethers monomers and polymers therefrom
US4420638A (en) * 1982-03-02 1983-12-13 E. I. Du Pont De Nemours And Company Fluorinated ether-ketones
US4686300A (en) * 1983-03-07 1987-08-11 E. I. Du Pont De Nemours And Company Polyfluoro gamma-ketoesters and 5-hydroxy gamma lactone analogues thereof
US4591439A (en) * 1984-05-08 1986-05-27 E. I. Du Pont De Nemours And Company Ion exchange process and apparatus
US5919973A (en) * 1996-12-02 1999-07-06 Shin-Etsu Chemical Co., Ltd. Process for the polymerization of hexafluoropropene oxide
US6407282B1 (en) * 1999-11-04 2002-06-18 Nippon Mektron, Limited Process for producing monoester from dicarboxylic acid fluoride
US7196235B2 (en) * 2001-06-29 2007-03-27 Asahi Kasei Kabushiki Kaisha Process for producing fluorinated vinyl ether
US20040176636A1 (en) * 2001-06-29 2004-09-09 Nobuto Hoshi Process for producing fluorinated vinyl ether
US20070167589A1 (en) * 2002-05-14 2007-07-19 Fernandez Richard E Fluorosulfates of hexafluoroisobutylene and its higher homologs and their derivatives
US20070167640A1 (en) * 2002-05-14 2007-07-19 Cherstkov Victor F Fluorosulfates of hexafluoroisobutylene and its higher homologs and their derivatives
US20040019237A1 (en) * 2002-05-14 2004-01-29 Cherstkov Victor Filippovich Fluorosulfates of hexafluoroisobutylene and its higher homologs
US20070167651A1 (en) * 2002-05-14 2007-07-19 Cherstkov Victor F Fluorosulfates of hexafluoroisobutylene and its higher homologs and their derivatives
US20070167652A1 (en) * 2002-05-14 2007-07-19 Cherstkov Victor F Fluorosulfates of hexafluoroisobutylene and its higher homologs and their derivatives
US7276624B2 (en) 2002-05-14 2007-10-02 E. I. Du Pont De Nemours And Company Fluorosulfates of hexafluoroisobutylene and its higher homologs
US7301059B2 (en) 2002-05-14 2007-11-27 E.I. Du Pont De Nemours And Company Fluorosulfates of hexafluoroisobutylene and its higher homologs and their derivatives
US7531689B2 (en) 2002-05-14 2009-05-12 E.I. Du Pont De Nemours And Company Fluorosulfates of hexafluoroisobutylene and its higher homologs and their derivatives
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US7579499B2 (en) 2002-05-14 2009-08-25 E. I. Du Pont De Nemours And Company Fluorosulfates of hexafluoroisobutylene and its higher homologs and their derivatives
US9765008B2 (en) 2014-01-10 2017-09-19 Unimatec Co., Ltd. Perfluorovinyloxy polyether carboxylic acid alkali metal salt and method for producing the same
CN114402011A (zh) * 2019-09-13 2022-04-26 大金工业株式会社 含氟代聚醚基化合物及其制造方法

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DE2817366A1 (de) 1978-10-26
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IT1094423B (it) 1985-08-02
NL187435C (nl) 1991-10-01
AU515564B2 (en) 1981-04-09
BR7802432A (pt) 1979-01-02
SU869555A3 (ru) 1981-09-30
BE866123A (fr) 1978-10-19
DE2817366C2 (zh) 1989-01-26
NZ187025A (en) 1979-06-19
MX172538B (es) 1993-12-17
SE436869B (sv) 1985-01-28
NL7804228A (nl) 1978-10-24
IT7822497A0 (it) 1978-04-19
FR2387938A1 (fr) 1978-11-17
SE7803062L (sv) 1978-10-21
FR2387938B1 (zh) 1984-08-10
JPS6049176B2 (ja) 1985-10-31
MX149082A (es) 1983-08-19
US4138426A (en) 1979-02-06
JPS53132519A (en) 1978-11-18
GB1593222A (en) 1981-07-15

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